Controlling ultrafast charge carrier dynamical processes at donor−acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable effect of hydrogen-bond formation and dynamics on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting π-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydrogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steady state and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between the donor and acceptor units. These recent results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor−acceptor interfaces but also in complex biological systems.